CN110057990A - A kind of pH bearing calibration of multi-parameter water quality section plotter - Google Patents
A kind of pH bearing calibration of multi-parameter water quality section plotter Download PDFInfo
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Abstract
The present invention relates to a kind of pH bearing calibrations of multi-parameter water quality section plotter, including the following steps: data acquisition: the pH section S of the observation each website in sea area is obtained using multi-parameter water quality section plotter；Data quality control: large amplitude singular value is removed by rejecting the temperature-sensitive data in instrument continuous mode, inverse pressure correction data, calculating Local standard deviation, quality control is carried out to S, Quality Control results are indicated with Q；Data are average: carrying out sliding average to erect-position downlink data each in Q, processing result is indicated with A；Data correction: on the basis of the seawater pH value for the desk-top pH meter measurement calibrated by pH standard buffer solution, processing is corrected to A.
Description
Technical field
The present invention relates to Marine Sciences fields, and in particular to a kind of pH correction of multi-parameter water quality section plotter (abbreviation RBR)
Method.
Background technique
PH indicates the negative logarithm (pH=log10 [H+]) of water middle acid substance hydrogen ion (H+) concentration, is used as water environment
The important indicator of health, is of great significance to the existence and procreation of marine organisms.About the measurement of seawater pH value, conventional chemical
Fado acquires water sample using hydrophore, and uses the pH value of desk-top pH meter measurement seawater.Due to desk-top pH meter probe price compared with
It is low, be easily changed, therefore measurement result is more accurate, but this method takes time and effort and can only obtain single-point pH data, has larger
Limitation.The appearance of multi-parameter water quality section plotter is acquisition high frequency and continuous cross-sectional data provides possibility, has become at present
For one of most widely used sea investigation instrument equipment in the world.The instrument is (deep comprising temperature, conductance (salinity), pressure
Degree), dissolved oxygen, effective photosynthesis irradiation (PAR), chlorophyll, turbidity, multiple probes such as pH, can at most measure 13 simultaneously
A underwater parameter.Due to its compact, be very suitable for coastal waters water body fast investigation, large area investigation, water quality profiling observation,
Boat observation, towed body installation observation, buoy long-term observation, seabed long term monitoring etc. are walked, but instrument works long hours or positioned at thermohaline
When being measured at spring layer, it is understood that there may be data wander or response lag phenomenon.It therefore, can be by two methods during field investigation
It combines, on the basis of the seawater pH value of desk-top pH meter measurement, school is carried out to the pH section of multi-parameter water quality section plotter observation
Just, the two mutual supplement with each other's advantages can obtain higher frequency and accurate pH section.
PH about multi-parameter water quality section plotter is corrected, and forefathers mostly use " linear regression method ", and considers multi-parameter water
The substantial measurement errors of matter section plotter pH probe, high pH is higher, and low pH is lower, i.e., slope changes in continuous mode, therefore should
The relative error of method is larger, therefore the present invention carries out school using the pH data that " ratio method " observes multi-parameter water quality section plotter
Just, it can obtain that precision is higher, pH section of better quality, provide good data for research seawater physicochemical property and support.
Summary of the invention
In view of this, improving the present invention provides a kind of pH bearing calibration of multi-parameter water quality section plotter because of instrument response
It drifts about at any time the evaluated error of generation, obtains the pH section of higher precision, provide higher frequency to study the physicochemical property of seawater
And accurate data basis.Technical scheme is as follows:
A kind of pH bearing calibration of multi-parameter water quality section plotter, including the following steps:
1) the pH section S of the observation each website in sea area data acquisition: is obtained using multi-parameter water quality section plotter；
2) data quality control: by rejecting the temperature-sensitive data in instrument continuous mode, inverse pressure correction data, calculating part
Standard deviation removal large amplitude singular value and etc., quality control is carried out to S, Quality Control results are indicated with Q；
3) data are average: carrying out sliding average to erect-position downlink data each in Q, processing result is indicated with A；
4) Data correction: on the basis of the seawater pH value for the desk-top pH meter measurement calibrated by pH standard buffer solution,
Processing is corrected to A, the method is as follows:
Step 1: removal spring layer data utilize the temperature of multi-parameter water quality section plotter simultaneous observation, salinity, the velocity of sound, the depth of water
Data calculate the buoyancy frequency N of each erect-position, and according to logN2> -3 determine the position of epilimnion in seawater, remove spring layer in A
The pH data at place, processing result indicate with T, the calculation formula of buoyancy frequency are as follows:
In formula, c0For the velocity of sound, ρ is density of sea water, and z is the depth of water, and g is acceleration of gravity, g2/co 2One magnitude is very small, suddenly
Slightly disregard；
Step 2: the seawater pH value of desk-top pH meter measurement and the ratio of pH in corresponding T are calculated, and the ratio is defined as
Ratio has:
In formula, pHbFor the seawater pH value of desk-top pH meter measurement, pHrRefer to the seawater of corresponding multi-parameter water quality section plotter measurement
PH value；
Step 3: it is assumed that Ratio approximation Normal Distribution, calculates the probability density function of Ratio, and to discrete larger
Ratio carry out 1~3 times of standard deviation and reject, processing result is indicated with R；
Step 4: data are observed with pH in corresponding T to R and carry out linear fit, the school of each erect-position pH section in calculating observation sea area
Positive coefficient, the method is as follows: enable y=ax+b, parameter a and b are used to adjust the slope and intercept of calibration curve, and x indicates multi-parameter water
The pH section A of matter section plotter observation, i.e., comprising whole pH data including spring layer, the corresponding correction ratio of the different pH of y expression；
Step 5: A is multiplied with y one-to-one correspondence, obtains complete pH correction section.
The pH bearing calibration of multi-parameter water quality section plotter of the invention, including data acquisition, data quality control, sliding are flat
Processing and Data correction.The pH section of the observation each website in sea area is obtained with multi-parameter water quality section plotter first；It connects down
To carry out data quality control, including removal temperature-sensitive data, inverse pressure correction data and deglitch three steps of processing；Then it uses
PH section after " moving average method " controls quality carries out average output；Finally using the pH value of desk-top pH meter measurement seawater as base
Standard averagely exports section to the pH of multi-parameter water quality section plotter observation and is corrected.The feature of the method for the present invention has: 1) multi-parameter
The sample frequency of water quality section plotter is 6Hz, available pH section more abundant；2) by pH aligning step, can improve
Because instrument response is drifted about the evaluated error of generation at any time, effectively guarantee the quality of data,It is provided for research seawater physicochemical property
Higher frequency and the support of accurate data.
Detailed description of the invention
Fig. 1 is pH bearing calibration flow chart
Fig. 2 is part of test results, in which:
(a) the spring layer sectional view of B09 erect-position
(b) probability density function and histogram frequency distribution diagram of Ratio
(c) Ratio and pHrLinear correlation curve
(d)pHbWith pHrLinear correlation curve
Fig. 3 is that yellow Bohai Sea in summer in 2017 shares the big mapping of flight number correction front and back bottom pH, in which:
(a) before correcting after (b) correction
Specific embodiment
The invention mainly comprises: data acquisition, data quality control, data are average and Data correction.Fig. 1 is provided
The block diagram of mentioned method.Include:
1, data acquisition: the pH section of the observation each website in sea area is obtained using multi-parameter water quality section plotter, and is indicated with S.
Instrument has used NIST (the National Institute of Standards of pH=4.01,7.00 and 9.21 before laying
And Technology, USA) standard buffer solution at room temperature to pH probe calibrated；Guarantee to lay during laying
Shipboard windward, is uniformly transferred, so as to instrument stabilizer measurement.The sample frequency of multi-parameter water quality section plotter is 6Hz, pH probe measurement
Range 1~13, precision 0.1 can obtain pH section more abundant；
2, data quality control: in order to exclude in observation process since ship motion, winch wirerope are swung and instrument is visited
Head unstability bring external interference needs to carry out quality control to the original pH section S that multi-parameter water quality section plotter measures,
Quality Control results are indicated with Q.Detailed process is as follows:
Step 1: removal temperature-sensitive data.Multi-parameter water quality section plotter need to stop about 1min at surface layer (~1m) after entering water, complete
At instrument temperature-sensitive process, this process is mostly false data, should give removal；
Step 2: inverse pressure correction data.Work as Pi-Pi-1≤ 0, reject PiPH data at the depth of water, in formula, i is a certain website
Data sequence, PiFor the pressure at i, Pi-1For the pressure at i-1；
Step 3: deglitch processing.PH section is calculated in the first derivative of corresponding depth and the Local standard deviation of derivative,
The signal that the two ratio is more than a certain given threshold is removed as spike, and is substituted with the average value of two end signal of spike.It is former
It manages as follows:
In formula, i is the data sequence of a certain website, ziFor the depth of water of corresponding position, xiIt is measured for multi-parameter water quality section plotter
Corresponding position pH data, DiFor the first derivative of corresponding depth, s is the standard deviation of corresponding depth first derivative.So thatWherein lim is variable, using the two ratio be more than lim this threshold value signal as spike removal, and with spike two
The average signal at end replaces.
3, data are average: in order to accurately indicate measurement result, random error caused by accidental fluctuation are eliminated, often to dynamic
Test data makees smooth and filtering processing.This patent is handled (processing result is indicated with A) to Q using " moving average method ",
0.2m physical phenomenon below is filtered out, to research and analyse in next step.The basic principle of moving average method:
yj=fj+ejJ=1,2 ..., N
In formula, yjFor dynamic test data, fiFor smoother measurement result, eiFor random error.
4, Data correction: to improve because instrument response is drifted about the evaluated error of generation at any time, the pH of higher precision is obtained
Section, mentioned method is on the basis of the seawater pH value that desk-top pH meter measures, to the pH section A of multi-parameter water quality section plotter observation
It is corrected.Detailed process is as follows:
Step 1: removal spring layer data.Thermohaline spring layer nearby due to water Inversion phenomenon suddenly and change dramatically, multi-parameter water quality
There may be response lag phenomenons for section plotter, therefore, it is necessary first to be removed to the pH data near each erect-position spring layer.
Using data such as the temperature of multi-parameter water quality section plotter simultaneous observation, salinity, the velocity of sound, the depth of waters, each erect-position is calculated
Buoyancy frequency N, and according to logN2> -3 determine the position of epilimnion in seawater, remove the pH data in A at spring layer, processing knot
Fruit is indicated with T.The calculation formula of buoyancy frequency are as follows:
In formula, c0For the velocity of sound, ρ is density of sea water, and z is the depth of water, and g is acceleration of gravity.g2/co 2One magnitude is very small, can
It ignores.
Step 2: the seawater pH value of desk-top pH meter measurement and the ratio of pH in corresponding T are calculated, and the ratio is defined as
Ratio has:
In formula, pHbFor the seawater pH value of desk-top pH meter measurement, pHrRefer to the seawater of corresponding multi-parameter water quality section plotter measurement
PH value.
Step 3: it is assumed that Ratio approximation Normal Distribution, calculates the probability density function of Ratio, and to discrete larger
Ratio carry out 1~3 times of standard deviation and reject, processing result is indicated with R.Based on above-mentioned it is assumed that will have 68% numeric distribution
There is the range within 1 standard deviation in distance average, about 95% numeric distribution has within 2 standard deviations in distance average
Range, about 99.7% numeric distribution have the range within 3 standard deviations in distance average.The calculation formula of probability density function
Are as follows:
It is denoted as X~N (μ, σ2),
Wherein, x is ratio R atio defined in step 2, and μ is the expectation of Ratio, and σ is the standard deviation of Ratio, σ2For
The variance of Ratio.
Step 4: data are observed with pH in corresponding T to R and carry out linear fit, the school of each erect-position pH section in calculating observation sea area
Positive coefficient.Y=ax+b is enabled, parameter a and b are used to adjust the slope and intercept of calibration curve, and x indicates that multi-parameter water quality section plotter is seen
The corresponding correction ratio of the different pH of pH section A, y expression of survey.This patent is right by taking yellow Bohai Sea in summer in 2017 shares flight number as an example
Discrete biggish Ratio makees 2 times of standard deviation rejecting processing, fitting gained unitary linearity curve are as follows:
Y=-0.0991x+1.8037 R2=0.8225
The Ratio and pH in regression curve it can be seen from R=0.9069rGood relationship, therefore use linear fitting
PH plane section correction suitable for multi-parameter water quality section plotter.
Step 5: A is multiplied with y one-to-one correspondence, obtains complete pH correction section.That is:
Y=A × y
In formula, A is the pH section of multi-parameter water quality section plotter observation before correcting, and Y is multi-parameter water quality section plotter after correction
The pH section of observation.
Linear fit is carried out to two sets of data of correction front and back, to examine whether pH correction front and back changes investigation sea area pH's
Spatial distribution, matched curve are as shown in Figure 2 d；Fig. 3 shows that the Bohai Sea Huanghai Sea summer in 2017 shares the big EDS maps of flight number bottom pH,
It can thus be seen that the spatial distribution of correction front and back pH does not change, but the quality of data significantly improves, and more meets normal
The scientific law that seawater pH is about 7.9~8.1.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (1)
1. a kind of pH bearing calibration of multi-parameter water quality section plotter, including the following steps:
1) the pH section S of the observation each website in sea area data acquisition: is obtained using multi-parameter water quality section plotter；
2) data quality control: by rejecting the temperature-sensitive data in instrument continuous mode, inverse pressure correction data, calculating local standard
Difference removal large amplitude singular value and etc., quality control is carried out to S, Quality Control results are indicated with Q；
3) data are average: carrying out sliding average to erect-position downlink data each in Q, processing result is indicated with A；
4) Data correction: on the basis of the seawater pH value for the desk-top pH meter measurement calibrated by pH standard buffer solution, to A into
Row correction process, the method is as follows:
Step 1: removal spring layer data, using the temperature of multi-parameter water quality section plotter simultaneous observation, salinity, the velocity of sound, bathymetric data,
The buoyancy frequency N of each erect-position is calculated, and according to logN2> -3 determine the position of epilimnion in seawater, remove in A at spring layer
PH data, processing result indicate with T, the calculation formula of buoyancy frequency are as follows:
In formula, c0For the velocity of sound, ρ is density of sea water, and z is the depth of water, and g is acceleration of gravity, g2/co 2One magnitude is very small, ignores not
Meter；
Step 2: calculating the seawater pH value of desk-top pH meter measurement and the ratio of pH in corresponding T, and the ratio be defined as Ratio,
Have:
In formula, pHbFor the seawater pH value of desk-top pH meter measurement, pHrRefer to the seawater pH value of corresponding multi-parameter water quality section plotter measurement；
Step 3: it is assumed that Ratio approximation Normal Distribution, calculates the probability density function of Ratio, and to discrete biggish
Ratio carries out 1~3 times of standard deviation and rejects, and processing result is indicated with R；
Step 4: data are observed with pH in corresponding T to R and carry out linear fit, the correction system of each erect-position pH section in calculating observation sea area
Number, the method is as follows: enable y=ax+b, parameter a and b are used to adjust the slope and intercept of calibration curve, and x indicates that multi-parameter water quality cuts open
The pH section A of face instrument observation, i.e., comprising whole pH data including spring layer, the corresponding correction ratio of the different pH of y expression；
Step 5: A is multiplied with y one-to-one correspondence, obtains complete pH correction section.
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| CN117405975A (en) * | 2023-12-14 | 2024-01-16 | 深圳鹏城新能科技有限公司 | Method, system and medium for detecting insulation resistance of PV panel |
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